WO1998007026A1 - Process and facility for examining chemical reactions in miniaturized reactors arranged parallel to each other - Google Patents

Process and facility for examining chemical reactions in miniaturized reactors arranged parallel to each other Download PDF

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Publication number
WO1998007026A1
WO1998007026A1 PCT/EP1997/004369 EP9704369W WO9807026A1 WO 1998007026 A1 WO1998007026 A1 WO 1998007026A1 EP 9704369 W EP9704369 W EP 9704369W WO 9807026 A1 WO9807026 A1 WO 9807026A1
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Prior art keywords
reactors
reactions
analysis
reaction
miniaturized
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PCT/EP1997/004369
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German (de)
French (fr)
Inventor
Norbert Windhab
Christian Miculka
Hans-Ulrich Hoppe
Original Assignee
Aventis Research & Technology Gmbh & Co Kg
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Application filed by Aventis Research & Technology Gmbh & Co Kg filed Critical Aventis Research & Technology Gmbh & Co Kg
Priority to DE59712908T priority Critical patent/DE59712908D1/en
Priority to AU43796/97A priority patent/AU731245B2/en
Priority to CA002263212A priority patent/CA2263212C/en
Priority to US09/242,199 priority patent/US6576470B1/en
Priority to JP50828398A priority patent/JP2001506743A/en
Priority to EP97941933A priority patent/EP1012598B1/en
Publication of WO1998007026A1 publication Critical patent/WO1998007026A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00306—Reactor vessels in a multiple arrangement
    • B01J2219/00313—Reactor vessels in a multiple arrangement the reactor vessels being formed by arrays of wells in blocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00585—Parallel processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00596—Solid-phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00659—Two-dimensional arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/0068—Means for controlling the apparatus of the process
    • B01J2219/00702—Processes involving means for analysing and characterising the products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B01J2219/00747—Catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00835—Comprising catalytically active material
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B30/00—Methods of screening libraries
    • C40B30/08—Methods of screening libraries by measuring catalytic activity
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/18—Libraries containing only inorganic compounds or inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries

Definitions

  • the invention relates to a method for the investigation of chemical reactions in the presence of potentially catalytic substances, in which the reactions are carried out in parallel in reactors.
  • the invention further relates to a device, in particular for carrying out this method, the device having a plurality of reactors connected in parallel, which are provided with feed and discharge lines.
  • the invention was therefore based on the object of developing an inexpensive method or an inexpensive device, with which a large number of chemical reactions can be investigated in a short time and thereby reproducible, qualitative and quantitative data regarding the composition of the different reaction mixtures and reaction products can be obtained.
  • This object is achieved by a process of the type mentioned at the outset, which is characterized in that the reactions are carried out in miniaturized reactors and the type and amount of the reaction mixture or the reaction products is analyzed during the reaction time.
  • the object is also achieved by a device of the type mentioned, which is characterized in that the reactors are miniaturized, with a volume in the range from 0.001 cm 3 to 1 cm 3 .
  • the invention thus relates to a method for the investigation of chemical reactions in the presence of potentially catalytic substances, in which the reactions are carried out in parallel in reactors, characterized in that the reactions are carried out in miniaturized reactors and the reaction mixture during the reaction time by type and amount analyzed.
  • the invention also relates to a device, in particular for carrying out this method, the device having a plurality of reactors connected in parallel, which are provided with feed and discharge lines, characterized in that the reactors are miniaturized, with a volume in the range from 0.001 cm 3 to 1 cm 3 .
  • a special embodiment of the process according to the invention is characterized in that the reaction starting materials are continuously fed to the reactors and the reaction products are continuously removed from the reactors. Batch control is also possible.
  • educts are used which are at least partially labeled with isotopes, preferably with deuterium ( 2 H) or heavy oxygen ( 18 O) or heavy carbon ( 13 C) or mixtures thereof. These generate characteristic spectral shifts in rotational vibration spectra, which, in addition to the reaction path marking using educt mixture variants, can lead to new, interesting reactions or reaction products and systematically contrasts smaller fractions of by-products.
  • Different reactant mixtures can also be supplied to individual reactors or to reactors combined in groups, in order to use the methods of combinatorial chemistry to recognize or discover any synergies that may be present.
  • the starting material, reaction or product mixtures can be analyzed by means of spectroscopic analysis, preferably by means of infrared spectroscopy (IR), particularly preferably by means of Fourier IR spectroscopy at any time during the course of the reaction according to the type and amount of the substances contained.
  • IR infrared spectroscopy
  • Other spectroscopic methods such as laser or UV spectroscopy are also suitable for the investigation.
  • the process can be carried out at different temperatures and pressures, at temperatures in the range from -50 ° C. up to and including 600 ° C., preferably from room temperature to 500 ° C., or at different pressures, at absolute pressures from 10 ' to 10 3 bar , preferably from 10 "2 to 200 bar.
  • the data obtained can then be a comprehensive parameter and Data analysis can be supplied.
  • the invention is further characterized in that the reactions can be carried out in the presence of a heterogeneous or homogeneous catalyst and in that the screening of the catalytic activity (ie product detection) and selectivity (main product distribution) of catalyst amounts less than 10 mg, preferably less than 1 mg, in one Reactor is possible.
  • a plurality of separate, miniaturized reactors can be arranged in one block.
  • the volume of these reactors can be in the range from 0.001 cm 3 to 1 cm 3 , preferably from 0.01 cm 3 to 0.5 cm 3 , particularly preferably from 0.05 cm 3 to 0.2 cm 3 .
  • the reactors are arranged as a square or rectangular pattern in a metal block, which can be cuboid or cube-shaped.
  • the metal block can be provided with heating block or cooling elements and can be equipped with a temperature sensor in the vicinity of each reactor. This enables controlled and reproducible temperature control. For example, a defined temperature gradient can be set via the metal block.
  • the reactors are advantageously arranged in a plane which is parallel to a surface of the cuboid.
  • the feed and discharge lines of the individual reactors are advantageously at least partially perpendicular to this plane. They can be designed as through holes in the metal block.
  • the reactors can be designed as bores.
  • the number of reactors in a block can be greater than 20, preferably greater than 40, particularly preferably greater than 100, very particularly preferably greater than 200.
  • small amounts of potential catalysts also called samples below
  • the reactors can be charged with catalysts automatically, preferably by a laboratory robot or a pipettor.
  • the miniaturized reactors in the metal block are designed as 4 mm bores and are arranged in such a way that they can be flowed through through 2.5 m capillary bores with different educt and inert gases.
  • the gases then pass into a spacer, preferably a spacer plate, which is placed on the metal block and in which the holes in the metal block continue.
  • the arrangement of metal block and spacer is provided with a common cuvette hole in which the gases can be analyzed spectroscopically. For this purpose, the hole is closed at both ends with a transparent window. If you want to analyze with infrared spectroscopy, windows made of 1 -1 -1 silicon, NaCI, KBr, Ge, ZnSe or KSR5 are preferred.
  • a collimated analysis beam in the case of IR spectroscopy, an infrared beam, preferably mirror-free, is coupled out of an interferometer and directed through dry-gas-flushed space through the cuvette bore to a detector behind it.
  • the cuvette bore can be 5 mm thick, for example. By choosing a suitable thick spacer, the length of the cuvette bore can be selected between a few cm (1 -10) and several 10 cm (10-50), depending on the reaction conditions and reaction type.
  • the analysis beam can be directed through all the cuvette bores in succession by means of a deflection device. However, several beams or several analyzers can also be used, so that a simultaneous recording of spectra with several reactors is possible.
  • the block with the reactors can also be moved by means of movement devices, for example stepper motors, in such a way that all the cuvette bores are successively in the beam path of the Spectrometer are brought.
  • Suitable materials for the block and spacers are preferably the customary, corrosion-resistant metallic materials familiar to the person skilled in the art, in particular aluminum or steel, preferably resistant to rust and / or acid and / or high temperatures.
  • a further embodiment of the device according to the invention which is particularly suitable for homogeneous catalysis, is characterized in that an ATR crystal (attenuated total reflection spectroscopy, preferably conically pointed) is used in at least one reactor with a volume that is preferably less than 200 ⁇ l , preferably made of ZnSe or made of KSR5 or made of diamond) enables the spectroscopic contact to the reaction mixture under different solvents and reaction conditions and pressures up to 200 bar.
  • the analysis beam is focused on the ATR crystal.
  • the advantages of the method and the device according to the invention are essentially that a large number of reactions can be carried out quickly, inexpensively and reproducibly under practically identical conditions and with comparatively small amounts of substance and sample and at the same time can be examined spectroscopically. It thus offers the possibility of using the possibilities discussed in the context of combinatorial chemistry (K. Burgess et al., Ang. Chem. 1996, 108, 2, 192, integrated into the application by reference) for industrial catalyst screening. By choosing identical samples and different other reaction conditions such as temperature, pressure, reactant composition, a parallel reaction optimization can be carried out.
  • a data matrix is advantageously set up in such a way that all selectable and documentable reaction conditions (educt partial pressures, educt composition, temperature, flow or flow rate, total pressure, Sample composition, sample grid parameters and all reference points of the spectra) according to reaction conditions, ie per reactor, are shown as columns of the matrix.
  • This matrix can be subjected to a factor analysis (ER Malinowski et. Al., Factor Analysis in Chemistry, Wiley, New York, 1980, incorporated by reference into the application) by using the covariance matrix, the eigenvalues, the abstract eigenvectors, the loads and the coefficients of the multidimensional regression are calculated and preferably output as files.
  • a (pre) normalization of the data by means of the mean "0" and standard deviations "1" can also be selected, as a result of which baseline or absolute magnitude effects can be avoided.
  • This allows the prediction of different sizes from calibration data sets (such as quantitative CO 2 components at different temperatures), the determination of the dependency on parameters in spectral ranges to optimize the analysis, the generation of different distance matrices from the output data (e.g. the similarity of catalysts with respect to the selected ones Sizes and properties) and the direct feedback of the catalyst composition onto a synthesis laboratory robot, which mixes a set of new catalyst samples, and synthesized "independently” by sintering or calcining on a robot line.
  • Fig. 1 is a schematic representation of the device according to the invention
  • Fig. 2 shows a single reactor 2 from the device according to the invention
  • a device 1 for examining chemical reactions essentially consists of a block-shaped arrangement 3 of miniaturized reactors 2.
  • the block-shaped arrangement 3 is designed in such a way that the reactors 2 are in a cuboid metal block 4 which has a front side 6 and a rear side 7 , are incorporated in the form of bores.
  • the reactors 2 are sunk into the front side 6 of the cuboid metal block 4 and arranged in a rectangular pattern. They are connected to holes 5 for feeding the educts.
  • Catalysts 8 are introduced into the reactors 2.
  • a spacer plate 9, in which the reactors 2 continue as bores, is applied to the front side 6 as a spacer.
  • a spacer plate 1 2 is arranged as a further spacer.
  • the cuvette bore 1 1 continues through the metal block 4 through to the spacer plate 1 2. It is closed on the free surfaces of the spacer plates with transparent windows 13 and serves to discharge the reaction products and at the same time as space for their spectroscopic analysis by means of an IR beam 14.
  • the reaction products, coming from the reactor 2 are passed through the holes 10 according to the arrows shown , 1 1 passed. From the end of the cuvette hole 1 1 in the spacer plate 1 2, they are derived via holes 15. In the vicinity of the reactors 2, heating elements 17 and thermocouples 18 are introduced into the metal block 4.
  • the block-shaped arrangement 3 can be moved in both spatial directions perpendicular to the IR beam 14 by stepper motors 16. This can each cuvette bore 1 1 belonging to one of the reactors 2 is moved into the IR beam.
  • the analysis of the IR beam is carried out by recording the interferogram using interferometer 20 and detector 19, which are arranged near the transparent windows 13.

Abstract

The invention pertains to a process for examining chemical reactions in the presence of potentially catalytical substance, wherein reactions are triggered in miniaturized reactors arranged parallel to each other and the nature and amount of the reaction mixture are analyzed during the reaction time. A facility involving reactors provided with inlet pipes and by-passes has miniaturized reactors wiht volumes of 0,001 cm3 to 1 cm3. Said invention allows for effecting a large number of reactions under virtually identical conditions and with a relatively low amount of substance and samples, at an attractive cost and in a reproducible manner, and simultaneous spectroscopic analysis. It also provides a means of using for industrial catalyst screening the possibilities discussed in relation to combinatorial chemistry. Choosing identical samples and other different reaction conditions ensures optimized parallel reactions.

Description

Beschreibungdescription
Verfahren und Vorrichtung zum Untersuchen von chemischen Reaktionen in parallel geschalteten, miniaturisierten ReaktorenMethod and device for investigating chemical reactions in miniaturized reactors connected in parallel
Die Erfindung betrifft ein Verfahren zur Untersuchung von chemischen Reaktionen in Gegenwart von potentiell katalytischen Substanzen, bei dem man die Reaktionen parallel in Reaktoren durchführt. Die Erfindung betrifft weiterhin eine Vorrichtung, insbesondere zur Durchführung dieses Verfahrens, wobei die Vorrichtung mehrere, parallel geschaltete Reaktoren aufweist, die mit Zu- und Ableitungen versehen sind.The invention relates to a method for the investigation of chemical reactions in the presence of potentially catalytic substances, in which the reactions are carried out in parallel in reactors. The invention further relates to a device, in particular for carrying out this method, the device having a plurality of reactors connected in parallel, which are provided with feed and discharge lines.
Verfahren und Vorrichtungen der genannten Art sind bekannt und werden unter anderem bei der Suche nach Katalysatoren zur heterogenen oder homogenen Katalyse technischer, chemischer Prozesse eingesetzt. In jüngster Zeit ermöglichen es jedoch neue Techniken, Substanzen in hoher Zahl herzustellen, die potentielle Katalysatoren für eine Vielzahl von chemischen Prozessen sein könnten (P. G. Schultz et al., Science 1 995, 1738). Die Untersuchung dieser Vielzahl von potentiellen Katalysatoren ist mit den herkömmlichen seriellen Screening-Verfahren kaum mehr möglich, da diese Screening-Verfahren bezüglich Durchsatz und analytischer Auflösung sowie in der Reproduzierbarkeit limitiert sind. Oft werden für reines Aktivitätsscreening völlig unzureichend integrale Effekte wie Erwärmung des Katalysators etc. ohne direkte Produktgemisch- bzw. Effektivitätsanalyse herangezogen. Außerdem stellen die Optimierung der Bedingungen zur Katalysatoraktivierung und Prozessführung besondere Anforderungen an quantitative, analytische Verfahren und an die Reproduzierbarkeit der Reaktionsbedingungen.Methods and devices of the type mentioned are known and are used, inter alia, in the search for catalysts for the heterogeneous or homogeneous catalysis of technical, chemical processes. Recently, however, new techniques have made it possible to produce substances in large numbers which could be potential catalysts for a large number of chemical processes (P.G. Schultz et al., Science 1 995, 1738). The investigation of this large number of potential catalysts is hardly possible with the conventional serial screening methods, since these screening methods are limited in terms of throughput and analytical resolution as well as in reproducibility. Integral effects such as heating the catalyst etc. are often used inadequate for pure activity screening without direct product mixture or effectiveness analysis. In addition, the optimization of the conditions for catalyst activation and process control place special demands on quantitative, analytical processes and on the reproducibility of the reaction conditions.
Der Erfindung lag daher die Aufgabe zugrunde, ein kostengünstiges Verfahren oder eine kostengünstige Vorrichtung zu entwickeln, womit man eine Vielzahl von chemischen Reaktionen in kurzer Zeit untersuchen kann und dabei reproduzierbare, qualitative und quantitative Daten bezüglich der Zusammensetzung der unterschiedlichen Reaktionsgemische und Reaktionsprodukte gewinnen kann.The invention was therefore based on the object of developing an inexpensive method or an inexpensive device, with which a large number of chemical reactions can be investigated in a short time and thereby reproducible, qualitative and quantitative data regarding the composition of the different reaction mixtures and reaction products can be obtained.
Gelöst wird diese Aufgabe durch ein Verfahren der eingangs genannten Art, das dadurch gekennzeichnet ist, daß man die Reaktionen in miniaturisierten Reaktoren durchführt und das Reaktionsgemisch oder die Reaktionsprodukte während der Reaktionszeit nach Art und Menge analysiert.This object is achieved by a process of the type mentioned at the outset, which is characterized in that the reactions are carried out in miniaturized reactors and the type and amount of the reaction mixture or the reaction products is analyzed during the reaction time.
Die Aufgabe wird außerdem durch eine Vorrichtung der genannten Art gelöst, die dadurch gekennzeichnet ist, daß die Reaktoren miniaturisiert sind, bei einem Volumen aus dem Bereich von 0,001 cm3 bis 1 cm3.The object is also achieved by a device of the type mentioned, which is characterized in that the reactors are miniaturized, with a volume in the range from 0.001 cm 3 to 1 cm 3 .
Gegenstand der Erfindung ist somit ein Verfahren zur Untersuchung von chemischen Reaktionen in Gegenwart von potentiell katalytischen Substanzen, bei dem man die Reaktionen parallel in Reaktoren durchführt, dadurch gekennzeichnet, daß man die Reaktionen in miniaturisierten Reaktoren durchführt und das Reaktionsgemisch während der Reaktionszeit nach Art und Menge analysiert.The invention thus relates to a method for the investigation of chemical reactions in the presence of potentially catalytic substances, in which the reactions are carried out in parallel in reactors, characterized in that the reactions are carried out in miniaturized reactors and the reaction mixture during the reaction time by type and amount analyzed.
Gegenstand der Erfindung ist außerdem eine Vorrichtung, insbesondere zur Durchführung dieses Verfahrens, wobei die Vorrichtung mehrere, parallel geschaltete Reaktoren aufweist, die mit Zu- und Ableitungen versehen sind, dadurch gekennzeichnet, daß die Reaktoren miniaturisiert sind, bei einem Volumen aus dem Bereich von 0,001 cm3 bis 1 cm3.The invention also relates to a device, in particular for carrying out this method, the device having a plurality of reactors connected in parallel, which are provided with feed and discharge lines, characterized in that the reactors are miniaturized, with a volume in the range from 0.001 cm 3 to 1 cm 3 .
Besondere Ausführungsformen bzw. Ausgestaltungen der Erfindung ergeben sich aus den jeweiligen Unteransprüchen. Es können auch einzelne oder mehrere der in den Ansprüchen genannten Einzelmerkmale jeweils für sich erfindungsgemäße Lösungen darstellen, und es sind auch die Merkmale innerhalb der Anspruchskategorien beliebig kombinierbar.Particular embodiments or refinements of the invention result from the respective subclaims. One or more of the individual features mentioned in the claims can also be used individually represent solutions according to the invention, and the features within the claim categories can be combined as desired.
Eine besondere Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß man die Reaktionsedukte laufend den Reaktoren zuführt und die Reaktionsprodukte laufend aus den Reaktoren abführt. Die Batch-Fahrweise ist aber ebenfalls möglich.A special embodiment of the process according to the invention is characterized in that the reaction starting materials are continuously fed to the reactors and the reaction products are continuously removed from the reactors. Batch control is also possible.
Eine weitere besondere Ausführungsform ist dadurch gekennzeichnet, daß man Edukte verwendet, die mindestens teilweise mit Isotopen markiert sind, bevorzugt mit Deuterium (2H) oder schweren Sauerstoff (18O) oder schweren Kohlenstoff (13C) oder Mischungen davon. Diese erzeugen charakteristische Spektrahlverschiebungen in Rotations-Schwingungsspektren, was neben der Reaktionswegemarkierung durch Eduktgemischvarianten zu neuen, interessanten Reaktionen bzw. Reaktionsprodukten führen kann und kleinere Nebenproduktanteile systematisch kontrastiert.Another particular embodiment is characterized in that educts are used which are at least partially labeled with isotopes, preferably with deuterium ( 2 H) or heavy oxygen ( 18 O) or heavy carbon ( 13 C) or mixtures thereof. These generate characteristic spectral shifts in rotational vibration spectra, which, in addition to the reaction path marking using educt mixture variants, can lead to new, interesting reactions or reaction products and systematically contrasts smaller fractions of by-products.
Es können auch einzelnen oder zu Gruppen zusammengefaßten Reaktoren unterschiedliche Eduktgemische zugeführt werden, um so mit den Methoden der kombinatorischen Chemie eventuell vorhandene Synergien zu erkennen oder zu entdecken.Different reactant mixtures can also be supplied to individual reactors or to reactors combined in groups, in order to use the methods of combinatorial chemistry to recognize or discover any synergies that may be present.
Die Edukt-, Reaktions- bzw. Produktgemische können mittels spektroskopischer Analyse, bevorzugt mittels Infrarotspektroskopie (IR), besonders bevorzugt mittels Fourier IR-Spektroskopie zu beliebigen Zeitpunkten des Reaktionsverlaufs nach Art und Menge der enthaltenen Substanzen analysiert werden. Andere spektroskopische Methoden wie Laser- oder UV-Spektroskopie sind zur Untersuchung ebenfalls geeignet. Das Verfahren kann bei unterschiedlichen Temperaturen und Drücken durchgeführt werden, bei Temperaturen aus dem Bereich von -50 °C bis einschließlich 600°C, bevorzugt von Raumtemperatur bis 500 °C, oder bei unterschiedlichen Drücken, bei Absolutdrücken von 10'3 bis 103 bar, bevorzugt von 10"2 bis 200 bar. Die gewonnenen Daten können dann einer umfassenden Parameter- und Datenanalyse zugeführt werden.The starting material, reaction or product mixtures can be analyzed by means of spectroscopic analysis, preferably by means of infrared spectroscopy (IR), particularly preferably by means of Fourier IR spectroscopy at any time during the course of the reaction according to the type and amount of the substances contained. Other spectroscopic methods such as laser or UV spectroscopy are also suitable for the investigation. The process can be carried out at different temperatures and pressures, at temperatures in the range from -50 ° C. up to and including 600 ° C., preferably from room temperature to 500 ° C., or at different pressures, at absolute pressures from 10 ' to 10 3 bar , preferably from 10 "2 to 200 bar. The data obtained can then be a comprehensive parameter and Data analysis can be supplied.
Die Erfindung ist weiter dadurch gekennzeichnet, daß die Reaktionen in Gegenwart eines heterogenen oder homogenenKatalysators durchgeführt werden können und daß das Screening der katalytischen Aktivität (d.h. Produktnachweis) und Selektivität (Hauptproduktverteilung) von Katalysatormengen kleiner als 10 mg, bevorzugt kleiner als 1 mg, in einem Reaktor möglich ist.The invention is further characterized in that the reactions can be carried out in the presence of a heterogeneous or homogeneous catalyst and in that the screening of the catalytic activity (ie product detection) and selectivity (main product distribution) of catalyst amounts less than 10 mg, preferably less than 1 mg, in one Reactor is possible.
In einer besonderen Ausgestaltungsform der erfindungsgemäßen Vorrichtung können in einem Block mehrere, voneinander getrennte, miniaturisierte Reaktoren angeordnet sein. Das Volumen dieser Reaktoren kann im Bereich von 0,001 cm3 bis 1 cm3 , bevorzugt von 0,01 cm3 bis 0,5 cm3, besonders bevorzugt von 0,05 cm3 bis 0,2 cm3 sein. In einer weiteren bevorzugten Ausgestaltungsform der erfindungsgemäßen Vorrichtung sind die Reaktoren als quadratisches oder rechteckiges Muster in einem Metallblock angeordnet, der quader- oder würfelförmig sein kann. Der Metallblock kann mit Heizblock- oder Kühlelementen versehen sein und kann in der Nähe eines jeden Reaktors mit einem Temperaturfühler ausgestattet sein. Dies ermöglicht eine kontrollierte und reproduzierbare Temperaturführung. Beispielsweise kann dadurch ein definierter Temperaturgradient über den Metallblock eingestellt werden. Die Reaktoren sind vorteilhafterweise in einer Ebene, die parallel zu einer Oberfläche des Quaders liegt, angeordnet. Die Zu- und Ableitungen der einzelnen Reaktoren liegen vorteilhafterweise zumindest teilweise senkrecht zu dieser Ebene. Sie können in dem Metallblock als durchgehende Bohrungen ausgeführt sein. Die Reaktoren können als Bohrungen ausgeführt sein. Die Zahl der Reaktoren in einem Block kann größer sein als 20, bevorzugt größer als 40, besonders bevorzugt größer als 100, ganz besonders bevorzugt größer als 200. Mit diesen Reaktoren können unter definierten Reaktionsbedingungen kleine Menge potentieller Katalysatoren (im folgenden auch Proben genannt) parallel, d.h. gleichzeitig mit Edukt bzw. Eduktgemischen in flüssiger und/oder in gasförmiger Form diskontinuierlich oder kontinuierlich in Kontakt und zur Reaktion gebracht werden. Eine Automatisierung der erfindungsgemäßen Vorrichtung ist möglich, insbesondere kann das Beschicken der Reaktoren mit Katalysatoren automatisch, bevorzugt durch einen Laborroboter oder einen Pipettierer erfolgen.In a special embodiment of the device according to the invention, a plurality of separate, miniaturized reactors can be arranged in one block. The volume of these reactors can be in the range from 0.001 cm 3 to 1 cm 3 , preferably from 0.01 cm 3 to 0.5 cm 3 , particularly preferably from 0.05 cm 3 to 0.2 cm 3 . In a further preferred embodiment of the device according to the invention, the reactors are arranged as a square or rectangular pattern in a metal block, which can be cuboid or cube-shaped. The metal block can be provided with heating block or cooling elements and can be equipped with a temperature sensor in the vicinity of each reactor. This enables controlled and reproducible temperature control. For example, a defined temperature gradient can be set via the metal block. The reactors are advantageously arranged in a plane which is parallel to a surface of the cuboid. The feed and discharge lines of the individual reactors are advantageously at least partially perpendicular to this plane. They can be designed as through holes in the metal block. The reactors can be designed as bores. The number of reactors in a block can be greater than 20, preferably greater than 40, particularly preferably greater than 100, very particularly preferably greater than 200. Under defined reaction conditions, small amounts of potential catalysts (also called samples below) can run in parallel with these reactors , ie at the same time with educt or educt mixtures in liquid and / or in gaseous form, discontinuously or continuously in contact and for Response. Automation of the device according to the invention is possible; in particular, the reactors can be charged with catalysts automatically, preferably by a laboratory robot or a pipettor.
In einer weiteren besonderen Ausgestaltungsform sind die miniaturisierten Reaktoren in dem Metallblock als 4 mm-Bohrungen ausgeführt und so angeordnet, daß sie durch 2,5-mrτvKapillarbohrungen mit unterschiedlichen Edukt- und Inertgasen beströmt werden können. Die Gase gelangen anschließend in einen Abstandshalter, vorzugsweise eine Distanzplatte, die auf den Metallblock aufgesetzt ist und in der sich die Bohrungen des Metallblocks fortsetzen. Die Anordnung aus Metallblock und Abstandshalter ist mit einer gängigen Küvettenbohrung versehen, in der die Gase spektroskopisch analysiert werden können. Dazu ist die Bohrung an beiden Enden mit einem transparenten Fenster verschlossen. Will man mit Infrarotspektroskopie analysieren, verwendet man bevorzugt Fenster aus 1 -1 -1 -Silicium, NaCI, KBr, Ge, ZnSe oder KSR5. Zur Analyse wird ein kollimierter Analysestrahl, bei IR-Spektroskopie ein Infrarotstrahl, bevorzugt spiegelfrei aus einem Interferometer ausgekoppelt und durch Trockengas-gespülten Raum durch die Küvettenbohrung auf einen dahinter liegenden Detektor gelenkt. Die Küvettenbohrung kann beispielsweise 5 mm dick sein. Durch die Wahl eines geeigneten dicken Abstandhalters kann die Länge der Küvettenbohrung zwischen wenigen cm (1 -10) und mehreren 10 cm (10-50) gewählt werden, je nach Reaktionsbedingungen und Reaktionstyp. Zur Aufnahme der Spektren kann der Analysestrahl mittels einer Ablenkvorrichtung nacheinander durch alle Küvettenbohrungen gelenkt werden. Es können aber auch mehrere Strahlen bzw. mehrere Analysatoren verwendet werden, so daß eine gleichzeitige Aufnahme von Spektren mit mehreren Reaktoren möglich ist. Es kann aber ebenso der Block mit den Reaktoren mittels Bewegungseinrichtungen, beispielsweise Schrittmotoren, so bewegt werden, daß alle Küvettenbohrungen nacheinander in den Strahlengang des Spektrometers gebracht werden. Als Werkstoffe für Block und Abstandshalter eignen sich vorzugsweise die gängigen, dem Fachmann geläufigen korrosionsbeständigen metallischen Werkstoffe, besonders Aluminium oder Stahl, vorzugsweise rost- und/oder säure- und/oder hochtemperaturbeständig.In a further special embodiment, the miniaturized reactors in the metal block are designed as 4 mm bores and are arranged in such a way that they can be flowed through through 2.5 m capillary bores with different educt and inert gases. The gases then pass into a spacer, preferably a spacer plate, which is placed on the metal block and in which the holes in the metal block continue. The arrangement of metal block and spacer is provided with a common cuvette hole in which the gases can be analyzed spectroscopically. For this purpose, the hole is closed at both ends with a transparent window. If you want to analyze with infrared spectroscopy, windows made of 1 -1 -1 silicon, NaCI, KBr, Ge, ZnSe or KSR5 are preferred. For analysis, a collimated analysis beam, in the case of IR spectroscopy, an infrared beam, preferably mirror-free, is coupled out of an interferometer and directed through dry-gas-flushed space through the cuvette bore to a detector behind it. The cuvette bore can be 5 mm thick, for example. By choosing a suitable thick spacer, the length of the cuvette bore can be selected between a few cm (1 -10) and several 10 cm (10-50), depending on the reaction conditions and reaction type. To record the spectra, the analysis beam can be directed through all the cuvette bores in succession by means of a deflection device. However, several beams or several analyzers can also be used, so that a simultaneous recording of spectra with several reactors is possible. However, the block with the reactors can also be moved by means of movement devices, for example stepper motors, in such a way that all the cuvette bores are successively in the beam path of the Spectrometer are brought. Suitable materials for the block and spacers are preferably the customary, corrosion-resistant metallic materials familiar to the person skilled in the art, in particular aluminum or steel, preferably resistant to rust and / or acid and / or high temperatures.
Eine weitere Ausgestaltung der erfindungsgemäßen Vorrichtung, die sich besonders für die homogene Katalyse eignet, ist dadurch gekennzeichnet, daß bei mindestens einem Reaktor mit einem Volumen, das bevorzugt kleiner als 200 μl ist, ein ATR-Kristall (Attenuated Total Reflection Spectroscopy, bevorzugt konisch spitz, bevorzugt aus ZnSe oder aus KSR5 oder aus Diamant) den spektroskopischen Kontakt zum Reaktionsgemisch bei unterschiedlichen Lösungsmitteln und Reaktionsbedingungen und Drücken bis 200 bar ermöglicht. In diesem Fall wird der Analysestrahl auf den ATR-Kristall fokussiert.A further embodiment of the device according to the invention, which is particularly suitable for homogeneous catalysis, is characterized in that an ATR crystal (attenuated total reflection spectroscopy, preferably conically pointed) is used in at least one reactor with a volume that is preferably less than 200 μl , preferably made of ZnSe or made of KSR5 or made of diamond) enables the spectroscopic contact to the reaction mixture under different solvents and reaction conditions and pressures up to 200 bar. In this case, the analysis beam is focused on the ATR crystal.
Die Vorteile des erfindungsgemäßen Verfahrens und der erfindungsgemäßen Vorrichtung liegen im wesentlichen darin, daß eine Vielzahl von Reaktionen unter praktisch identischen Bedingungen und mit vergleichsweise geringen Substanz- und Probenmengen schnell, kostengünstig und reproduzierbar durchgeführt und dabei gleichzeitig spektroskopisch untersucht werden kann. Sie bietet damit die Möglichkeit, die im Zusammenhang mit der kombinatorischen Chemie diskutierten Möglichkeiten (K. Burgess et al., Ang. Chem. 1996, 108, 2, 192, durch Bezugnahme mit in die Anmeldung integriert) für ein industrielles Katalysatorscreening einzusetzen. Durch die Wahl identischer Proben und unterschiedlicher sonstiger Reaktionsbedingungen wie Temperatur, Druck, Eduktzusammensetzung kann eine parallele Reaktionsoptimierung durchgeführt werden.The advantages of the method and the device according to the invention are essentially that a large number of reactions can be carried out quickly, inexpensively and reproducibly under practically identical conditions and with comparatively small amounts of substance and sample and at the same time can be examined spectroscopically. It thus offers the possibility of using the possibilities discussed in the context of combinatorial chemistry (K. Burgess et al., Ang. Chem. 1996, 108, 2, 192, integrated into the application by reference) for industrial catalyst screening. By choosing identical samples and different other reaction conditions such as temperature, pressure, reactant composition, a parallel reaction optimization can be carried out.
Zur Analyse der gewonnenen Daten wird vorteilhafterweise eine Datenmatrix dergestalt aufgestellt, daß alle wählbaren und dokumentierbaren Reaktionsbedingungen (Edukt-Partialdrücke, Eduktzusammensetzung, Temperatur, Durchfluß bzw. Durchflußrate, Gesamtdruck, Probenzusammensetzung, Probengitterparameter und alle Stützstellen der Spektren) nach Reaktionsbedingungen, d.h. je Reaktor, als Spalten der Matrix dargestellt werden. Diese Matrix kann einer Faktorenanalyse (E.R. Malinowski et. al., Factor Analysis in Chemistry, Wiley, New York, 1980, durch Bezugnahme mit in die Anmeldung integriert) unterzogen werden, indem man die Covarianzmatrix, die Eigenwerte, die abstrakten Eigenvektoren, die Loadings sowie die Koeffizienten der mehrdimensionalen Regression berechnet und bevorzugt als Dateien ausgibt. Es kann auch eine (Vor-)Normalisierung der Daten durch den Mittelwert "0" und Standardabweichungen "1 " gewählt werden, wodurch Grundlinien- oder Absolutbetrageffekte vermieden werden können. Dies erlaubt die Vorhersage verschiedener Größen aus Eichdatensätzen (wie z.B. quantitative CO2-Anteile bei verschiedenen Temperaturen), die Bestimmung der Abhängigkeit von Parametern in Spektralbereichen zur Optimierung der Analytik, die Generierung unterschiedlicher Distanzmatrizen aus den Ausgangsdaten (beispielsweise die Ähnlichkeit von Katalysatoren bezüglich der ausgewählten Größen und Eigenschaften) und das direkte Rückkoppeln der Katalysatorzusammensetzung auf einen Syntheselaborroboter, der einen Satz neuer Katalysatorproben mischt, und durch Sintern bzw. Kalzinieren auf einer Roboterstraße "selbständig" synthetisiert.To analyze the data obtained, a data matrix is advantageously set up in such a way that all selectable and documentable reaction conditions (educt partial pressures, educt composition, temperature, flow or flow rate, total pressure, Sample composition, sample grid parameters and all reference points of the spectra) according to reaction conditions, ie per reactor, are shown as columns of the matrix. This matrix can be subjected to a factor analysis (ER Malinowski et. Al., Factor Analysis in Chemistry, Wiley, New York, 1980, incorporated by reference into the application) by using the covariance matrix, the eigenvalues, the abstract eigenvectors, the loads and the coefficients of the multidimensional regression are calculated and preferably output as files. A (pre) normalization of the data by means of the mean "0" and standard deviations "1" can also be selected, as a result of which baseline or absolute magnitude effects can be avoided. This allows the prediction of different sizes from calibration data sets (such as quantitative CO 2 components at different temperatures), the determination of the dependency on parameters in spectral ranges to optimize the analysis, the generation of different distance matrices from the output data (e.g. the similarity of catalysts with respect to the selected ones Sizes and properties) and the direct feedback of the catalyst composition onto a synthesis laboratory robot, which mixes a set of new catalyst samples, and synthesized "independently" by sintering or calcining on a robot line.
Im folgenden wird eine Ausführungsform des erfindungsgemäßen Verfahrens und eine Ausgestaltung der erfindungsgemäßen Vorrichtung anhand der Figuren 1 bis 2 näher erläutert, ohne daß dadurch beabsichtigt ist, die Erfindung in irgendeiner Weise zu beschränken. Es zeigtIn the following, an embodiment of the method according to the invention and an embodiment of the device according to the invention are explained in more detail with reference to FIGS. 1 to 2, without this being intended to restrict the invention in any way. It shows
Fig. 1 eine schematische Darstellung der erfindungsgemäßen VorrichtungFig. 1 is a schematic representation of the device according to the invention
1 im Strahlengang eines spektroskopischen Analysators; Fig. 2 einen einzelnen Reaktor 2 aus der erfindungsgemäßen Vorrichtung1 in the beam path of a spectroscopic analyzer; Fig. 2 shows a single reactor 2 from the device according to the invention
1 in seitlicher Schnittansicht.1 in a sectional side view.
Eine Vorrichtung 1 zur Untersuchung von chemischen Reaktionen besteht im wesentlichen aus einer blockförmigen Anordnung 3 von miniaturisierten Reaktoren 2. Die blockförmige Anordnung 3 ist in der Weise ausgeführt, daß die Reaktoren 2 in einem quaderformigen Metallblock 4, der eine Vorderseite 6 und eine Rückseite 7 aufweist, in der Form von Bohrungen eingearbeitet sind. Die Reaktoren 2 sind in die Vorderseite 6 des quaderformigen Metallblocks 4 eingesenkt und in einem rechteckigem Muster angeordnet. Sie sind zum Zuführen der Edukte mit Bohrungen 5 verbunden. In die Reaktoren 2 sind Katalysatoren 8 eingebracht. Auf die Vorderseite 6 ist als Abstandshalter eine Distanzplatte 9 aufgebracht, in der sich die Reaktoren 2 als Bohrungen fortsetzen. Von diesen führen weitere Bohrungen 10, die der Ableitung der Reaktionsprodukte dienen, zu einer Küvettenbohrung 1 1 . Auf der Rückseite 7 ist als weiterer Abstandshalter eine Distanzplatte 1 2 angeordnet. Die Küvettenbohrung 1 1 setzt sich durch den Metallblock 4 hindurch bis durch die Distanzplatte 1 2 hindurch fort. Sie ist an den freien Oberflächen der Distanzplatten mit transparenten Fenstern 13 verschlossen und dient der Ableitung der Reaktionsprodukte und gleichzeitig als Raum für deren spektroskopische Analyse mittels eines IR Strahls 14. Die Reaktionsprodukte werden, vom Reaktor 2 kommend, entsprechend den eingezeichneten Pfeilen durch die Bohrungen 10, 1 1 geleitet. Vom Ende der Küvettenbohrung 1 1 in der Distanzplatte 1 2 werden sie über Bohrungen 15 abgeleitet. In der Nähe der Reaktoren 2 sind Heizelemente 1 7 und Thermoelemente 18 in den Metallblock 4 eingebracht. Die blockförmige Anordnung 3 ist durch Schrittmotoren 1 6 in beide Raumrichtungen senkrecht zum IR-Strahl 14 bewegbar. Dadurch kann jede zu einem der Reaktoren 2 gehörige Küvettenbohrung 1 1 in den IR-Strahl bewegt werden. Die Analyse des IR-Strahls erfolgt durch Aufnahme des Interferogramms mittels Interferometer 20 und Detektor 1 9, die nahe den transparenten Fenstern 13 angeordnet sind.A device 1 for examining chemical reactions essentially consists of a block-shaped arrangement 3 of miniaturized reactors 2. The block-shaped arrangement 3 is designed in such a way that the reactors 2 are in a cuboid metal block 4 which has a front side 6 and a rear side 7 , are incorporated in the form of bores. The reactors 2 are sunk into the front side 6 of the cuboid metal block 4 and arranged in a rectangular pattern. They are connected to holes 5 for feeding the educts. Catalysts 8 are introduced into the reactors 2. A spacer plate 9, in which the reactors 2 continue as bores, is applied to the front side 6 as a spacer. From these, further bores 10, which serve to discharge the reaction products, lead to a cuvette bore 11. On the back 7, a spacer plate 1 2 is arranged as a further spacer. The cuvette bore 1 1 continues through the metal block 4 through to the spacer plate 1 2. It is closed on the free surfaces of the spacer plates with transparent windows 13 and serves to discharge the reaction products and at the same time as space for their spectroscopic analysis by means of an IR beam 14. The reaction products, coming from the reactor 2, are passed through the holes 10 according to the arrows shown , 1 1 passed. From the end of the cuvette hole 1 1 in the spacer plate 1 2, they are derived via holes 15. In the vicinity of the reactors 2, heating elements 17 and thermocouples 18 are introduced into the metal block 4. The block-shaped arrangement 3 can be moved in both spatial directions perpendicular to the IR beam 14 by stepper motors 16. This can each cuvette bore 1 1 belonging to one of the reactors 2 is moved into the IR beam. The analysis of the IR beam is carried out by recording the interferogram using interferometer 20 and detector 19, which are arranged near the transparent windows 13.
Im folgenden wird ein Versuchsbeispiel mit einem bekannten Katalysator beschrieben.An experimental example using a known catalyst is described below.
In der erfindungsgemäßen Vorrichtung wurden in den Reaktoren des Reaktorblockes unterschiedliche Feststoffe mit einem Gemisch aus 30,2 Vol.-% Propylen 2.5, 1 5,2 Vol.-% Sauerstoff 4.5, Rest Stickstoff 5.0 beströmt. Einer der Rreaktoren enthielt eine kleine Menge (5 mg) eines bekannten, industriellen Katalysators für die Oxidation von Propylen zu Acrolein. Vollautomatisch wurden die IR-Spektren aller Reaktionsgase bei unterschiedlichen Temperaturen aufgenommen. Fig.3 zeigt das Spektrum des Reaktionsgases des Reaktors, der den bekannten Katalysator enthielt bei 400 und 450 °C: Bei 400 °C kann bereits das Produkt (Acrolein aus Sauerstoff und Propylen) nachgewiesen werden. Es entstand allerdings noch viel Kohlendioxid. Bei 450 °C wurde kein Kohlendioxid mehr festgestellt, die Ausbeute an Produkt hatte zugenommen. (Die leichte negative Bande entstand durch Referenzierung und gibt die Grundliniengenauigkeit in diesem Experiment wieder.)In the device according to the invention, different solids were streamed with a mixture of 30.2% by volume propylene 2.5, 1 5.2% by volume oxygen 4.5, the rest nitrogen 5.0 in the reactors of the reactor block. One of the reactors contained a small amount (5 mg) of a known industrial catalyst for the oxidation of propylene to acrolein. The IR spectra of all reaction gases were recorded fully automatically at different temperatures. 3 shows the spectrum of the reaction gas of the reactor which contained the known catalyst at 400 and 450 ° C.: The product (acrolein from oxygen and propylene) can already be detected at 400 ° C. However, a lot of carbon dioxide was still generated. At 450 ° C no more carbon dioxide was found, the yield of the product had increased. (The slight negative band was created by referencing and reflects the baseline accuracy in this experiment.)
Somit wurde gezeigt, daß eine Katalysatoraktivität für eine spezielle Reaktion vollautomatisch nachgewießen und optimiert werden kann. It has thus been shown that a catalyst activity for a special reaction can be re-weighed and optimized fully automatically.

Claims

Patentansprüche claims
1. Verfahren zur Untersuchung von chemischen Reaktionen in Gegenwart von potentiell katalytischen Substanzen, bei dem man die Reaktionen parallel in Reaktoren durchführt, dadurch gekennzeichnet, daß man die Reaktionen in miniaturisierten Reaktoren durchführt und das Reaktionsgemisch während der Reaktionszeit nach Art und Menge analysiert.1. A method for the investigation of chemical reactions in the presence of potentially catalytic substances, in which the reactions are carried out in parallel in reactors, characterized in that the reactions are carried out in miniaturized reactors and the reaction mixture is analyzed during the reaction time in terms of type and quantity.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß man die Reaktionsedukte laufend den Reaktoren zuführt und die Produkte laufend aus den Reaktoren abführt.2. The method according to claim 1, characterized in that the reactants are continuously fed to the reactors and the products are continuously removed from the reactors.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Reaktionen bei unterschiedlichen Temperaturen durchführt, vorzugsweise bei Temperaturen aus dem Bereich von Raumtemperatur bis einschließlich 600°C oder bei unterschiedlichen Drücken, vorzugsweise bei Absolutdrücken von 10"3 bis 103 bar, besonders bevorzugt von 10'2 bis 200 bar.3. The method according to claim 1 or 2, characterized in that one carries out the reactions at different temperatures, preferably at temperatures from the range from room temperature up to and including 600 ° C or at different pressures, preferably at absolute pressures of 10 "3 to 10 3 bar , particularly preferably from 10 ' to 200 bar.
4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die potentiellen Katalysatoren heterogene oder homogene Katalysatoren sind.4. The method according to one or more of claims 1 to 3, characterized in that the potential catalysts are heterogeneous or homogeneous catalysts.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man pro Reaktor eine Katalysatormenge < 10 mg, bevorzugt < 1 mg verwendet.5. The method according to claim 4, characterized in that one uses an amount of catalyst <10 mg, preferably <1 mg, per reactor.
6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man das Reaktionsgemisch oder die Reaktionsprodukte spektroskopisch nach Art und Menge der Bestandteile analysiert, vorzugsweise mit IR-Spektroskopie.6. The method according to one or more of claims 1 to 5, characterized in that the reaction mixture or the reaction products spectroscopically according to the type and amount of the constituents analyzed, preferably with IR spectroscopy.
7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Reaktionen in mehr als 20, bevorzugt mehr als 40, besonders bevorzugt mehr als 100 Reaktoren durchführt.7. The method according to one or more of claims 1 to 6, characterized in that one carries out the reactions in more than 20, preferably more than 40, particularly preferably more than 100 reactors.
8. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man Reaktionen der homogenen oder heterogenen Katalyse mit flüssigen oder gasförmigen Edukten oder Produkten untersucht.8. The method according to one or more of claims 1 to 6, characterized in that reactions of homogeneous or heterogeneous catalysis with liquid or gaseous starting materials or products are investigated.
9. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man die spektroskopische Analyse an allen Reaktoren gleichzeitig durchführt indem man eine entsprechende Zahl von Analysatoren einsetzt, oder daß man die spektroskopische Analyse an den Reaktoren nacheinander durchführt, in dem man einen Analysestrahl, mittels einer Ablenkvorrichtung nacheinander auf die einzelnen Reaktoren richtet oder indem man die Reaktoren mittels einer Bewegungseinrichtung nacheinander in den Analysestrahl bringt.9. The method according to claim 6, characterized in that one carries out the spectroscopic analysis on all reactors at the same time by using a corresponding number of analyzers, or that one carries out the spectroscopic analysis on the reactors in succession, in which an analysis beam, by means of a deflection device directed one after the other at the individual reactors or by bringing the reactors successively into the analysis beam by means of a moving device.
10. Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß man Edukte verwendet, die mindestens teilweise mit Isotopen markiert sind, bevorzugt mit Deuterium oder schweren Sauerstoff oder schweren Kohlenstoff.10. The method according to one or more of claims 1 to 9, characterized in that educts are used which are at least partially labeled with isotopes, preferably with deuterium or heavy oxygen or heavy carbon.
1 1 . Verfahren nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß einzelnen oder zu Gruppen zusammengefaßten Reaktoren unterschiedliche Eduktgemische zugeführt werden.1 1. Process according to one or more of Claims 1 to 10, characterized in that different reactant mixtures are fed to individual reactors or to reactors which are grouped together.
12. Vorrichtung, insbesondere zur Durchführung des Verfahrens gemäß Anspruch 1 , wobei die Vorrichtung mehrere, parallel geschaltete Reaktoren aufweist, die mit Zu- und Ableitungen versehen sind, dadurch gekennzeichnet, daß die Reaktoren miniaturisiert sind, bei einem Volumen aus dem Bereich von 0,001 cm3 bis 1 cm3.12. The device, in particular for performing the method according to Claim 1, wherein the device has a plurality of reactors connected in parallel, which are provided with feed and discharge lines, characterized in that the reactors are miniaturized, with a volume in the range from 0.001 cm 3 to 1 cm 3 .
13. Vorrichtung nach Anspruch 12, dadurch gekennzeichnet, daß die Reaktoren in der Form eines Blocks angeordnet sind, vorzugsweise rechteckig oder quadratisch.13. The apparatus according to claim 12, characterized in that the reactors are arranged in the form of a block, preferably rectangular or square.
14. Vorrichtung nach Anspruch 12 oder 13, dadurch gekennzeichnet, daß die Zuleitungen oder die Ableitungen oder die Reaktoren mindestens teilweise für Analysestrahlung, vorzugsweise für Infrarot-, Laser- oder UV-Licht transparent sind.14. The apparatus according to claim 12 or 13, characterized in that the feed lines or the discharge lines or the reactors are at least partially transparent to analysis radiation, preferably for infrared, laser or UV light.
15. Vorrichtung nach einem oder mehreren der Ansprüche 12 bis 14, dadurch gekennzeichnet, daß die Reaktoren in einem quaderformigen Metallblock angeordnet sind, der mit Heizelementen und/oder Temperaturmeßstellen ausgerüstet ist.15. The device according to one or more of claims 12 to 14, characterized in that the reactors are arranged in a cuboid metal block which is equipped with heating elements and / or temperature measuring points.
16. Vorrichtung nach einem oder mehreren der Ansprüche 1 2 bis 1 5, dadurch gekennzeichnet, daß die Vorrichtung mit Bewegungseinrichtungen versehen ist, vorzugsweise mit Schrittmotoren.16. The device according to one or more of claims 1 2 to 1 5, characterized in that the device is provided with movement devices, preferably with stepper motors.
17. Vorrichtung nach einem oder mehreren der Ansprüche 12 bis 16, dadurch gekennzeichnet, daß die Vorrichtung mehr als 20, bevorzugt mehr als 40, besonders bevorzugt mehr als 100, ganz besonders bevorzugt mehr als 200 Reaktoren aufweist.17. The device according to one or more of claims 12 to 16, characterized in that the device has more than 20, preferably more than 40, particularly preferably more than 100, very particularly preferably more than 200 reactors.
18. Vorrichtung nach einem oder mehreren der Ansprüche 12 bis 17, dadurch gekennzeichnet, daß mindestens ein Reaktor mit einem ATR- Kristall ausgerüstet ist, der einen spektroskopischen Kontakt zum Reaktionsgemisch ermöglicht.18. The device according to one or more of claims 12 to 17, characterized in that at least one reactor with an ATR Crystal is equipped, which allows a spectroscopic contact with the reaction mixture.
19. Vorrichtung nach Anspruch 15, dadurch gekennzeichnet, daß die Reaktoren in einer Ebene parallel zu einer Oberfläche des Metallblockes angeordnet sind, daß die Zu- oder Ableitungen mindestens abschnittsweise senkrecht zu dieser Ebene gelegt sind, daß auf der Oberfläche eine Abstandshalter angebracht ist, der Bohrungen aufweist, durch die die Reaktoren oder die Ableitungen verlängerbar sind, daß der Metallblock und die Abstandshalter Küvettenbohrungen aufweisen und daß auf der Abstandsplatte für Analysenstrahlung transparente Fenster angebracht sind, die die Küvettenbohrungen gegen die Umgebung verschließen.19. The apparatus according to claim 15, characterized in that the reactors are arranged in a plane parallel to a surface of the metal block, that the feed or discharge lines are at least partially perpendicular to this plane, that a spacer is attached to the surface, the Has holes through which the reactors or the leads are extendable, that the metal block and the spacers have cuvette holes and that transparent windows are attached to the spacer plate for analysis radiation, which close the cuvette holes from the environment.
20. Vorrichtung nach einem oder mehreren der Ansprüche 12 bis 19, dadurch gekennzeichnet, daß die Reaktoren Katalysatoren ebthalten, bevorzugt mit einem Gewicht kleiner als 10 mg pro Reaktor, besonders bevorzugt mit einem Gewicht kleiner als 1 mg pro Reaktor. 20. The device according to one or more of claims 12 to 19, characterized in that the reactors contain catalysts, preferably with a weight less than 10 mg per reactor, particularly preferably with a weight less than 1 mg per reactor.
PCT/EP1997/004369 1996-08-15 1997-08-12 Process and facility for examining chemical reactions in miniaturized reactors arranged parallel to each other WO1998007026A1 (en)

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DE59712908T DE59712908D1 (en) 1996-08-15 1997-08-12 METHOD AND DEVICE FOR EXAMINING CHEMICAL REACTIONS IN PARALLEL-SWITCHED, MINIATURIZED REACTORS
AU43796/97A AU731245B2 (en) 1996-08-15 1997-08-12 Process and apparatus for studying chemical reactions in parallel-connected miniaturized reactors
CA002263212A CA2263212C (en) 1996-08-15 1997-08-12 Process and apparatus for studying chemical reactions in parallel-connected miniaturized reactors
US09/242,199 US6576470B1 (en) 1996-08-15 1997-08-12 Process and facility for examining chemical reactions in miniaturized reactors arranged parallel to each other
JP50828398A JP2001506743A (en) 1996-08-15 1997-08-12 Method and apparatus for studying chemical reactions in miniaturized reactors connected in parallel
EP97941933A EP1012598B1 (en) 1996-08-15 1997-08-12 Process and facility for examining chemical reactions in miniaturized reactors arranged parallel to each other

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CA2263212C (en) 2006-03-14
ATE382859T1 (en) 2008-01-15
EP1012598B1 (en) 2008-01-02
JP2001506743A (en) 2001-05-22
US6576470B1 (en) 2003-06-10
DE59712908D1 (en) 2008-02-14
AU4379697A (en) 1998-03-06
DE19632779A1 (en) 1998-02-19
EP1012598A1 (en) 2000-06-28
AU731245B2 (en) 2001-03-29

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